Substituted aminophenyl carbamates

ABSTRACT

Fungicidal substituted aminophenyl carbamates of the formula ##STR1## in which X represents --CO--NR 8  R 9  ; --CO--OR 9  ; --CO--SR 9  ; --CO R   10  ; --SO 2  R 9  or hydrogen, in which 
     R 8  represents hydrogen or alkyl, 
     R 9  represents optionally substituted aryl, optionally substituted aralkyl, optionally substituted alkyl, alkenyl, halogenoalkenyl, or in each case optionally substituted cycloalkyl, cycloalkenyl or cycloalkylalkyl, and 
     R 10  has the meaning of R 9  or represents an optionally substituted heterocyclic ring, 
     Y 1  to Y 4  are identical or different and represent hydrogen, halogen, nitro, cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio, alkylsulfonyl or halogenoalkythio, 
     R 1  to R 7  are identical or different and represent hydrogen, alkyl, halogenoalkyl or alkoxyalkyl, 
     n represents 0 or 1, and 
     Z represents alkyl, halogenoalkyl or a ##STR2##  radical, in which R 11  to R 14  are identical or different and represent hydrogen, alkyl, halogenoalkyl or alkoxyalkyl, and 
     R 15  represents alkyl, halogenoalkyl or alkoxyalkyl.

The present invention relates to new aminophenyl carbamates, a processfor the preparation thereof, and the use thereof for combating pests.

It has already been disclosed that certain substituted 3-aminophenylcarbamates have good herbicidal properties (cf. U.S. Pat. No.3,832,389).

In addition, many phenyl carbamates which have a fungicidal action areknown (cf. EP 116,409; EP 117,024 and EP 125,901).

Further substituted aminophenyl carbamates are described in humanmedicine (cf. JP 57,007,459).

New aminophenyl carbamates of the general formula ##STR3## in which Xrepresents --CO--NR⁸ R⁹ ; --CO--OR⁹ ; --CO--SR⁹ ; --CO--R¹⁰ ; --SO₂ R⁹or hydrogen, in which

R⁸ represents hydrogen or alkyl,

R⁹ represents optionally substituted aryl, optionally substitutedaralkyl, optionally substituted alkyl, alkenyl, halogenoalkenyl, or ineach case optionally substituted cycloalkyl, cycloalkenyl orcycloalkylalkyl, and

R¹⁰ has the meaning of R⁹ or represents an optionally substitutedheterocyclic ring,

Y¹ to Y⁴ are identical or different and represent hydrogen, halogen,nitro, cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,alkylsulfonyl or halogenalkylthio,

R¹ to R⁷ are identical or different and represent hydrogen, alkyl,halogenoalkyl or alkoxyalkyl,

n represents 0 or 1, and

Z represents alkyl, halogenoalkyl or a ##STR4## radical, in which R¹¹ toR¹⁴ are identical or different and represent hydrogen, alkyl,halogenoalkyl or alkoxyalkyl, and

R¹⁵ represents alkyl, alkoxyalkyl or halogenoalkyl,

have been found.

The substituted aminophenyl carbamates of the formula (I) contain one ormore centers of asymmetry and can thus consist of diastereomers ormixtures of diastereomers, which are produced in different amountratios. They are produced mainly as racemates.

It has furthermore been found that the new substituted aminophenylcarbamates of the formula (I) ##STR5## in which X represents --CO--NR⁸R⁹ ; --CO--OR⁹ ; --CO--SR⁹ ; --CO--R¹⁰ ; --SO₂ R⁹ or hydrogen, in which

R⁸ represents hydrogen or alkyl,

R⁹ represents optionally substituted aryl, optionally substitutedaralkyl, optionally substituted alkyl, alkenyl, halogenoalkenyl, or ineach case optionally substituted cycloalkyl, cycloalkenyl orcycloalkylalkyl, and

R¹⁰ has the meaning of R⁹ or represents an optionally substitutedheterocyclic ring,

Y¹ to Y⁴ are identical or different and represent hydrogen, halogen,nitro, cyano, alkyl, halogenoalkyl, alkoxy, halogenoalkoxy, alkylthio,alkylsulfonyl or halogenoalkylthio,

R¹ to R⁷ are identical or different and represent hydrogen, alkyl,halogenoalkyl or alkoxyalkyl,

n represents 0 or 1, and

Z represents alkyl, halogenoalkyl or a ##STR6## radical, in which R¹¹ toR¹⁴ are identical or different and represent hydrogen, alkyl,halogenoalkyl or alkoxyalkyl, and

R¹⁵ represents alkyl, alkoxyalkyl or halogenoalkyl,

are obtained when aminophenols of the formula (II) ##STR7## in which Xand Y¹ to Y⁴ have the abovementioned meanings,

(a) are reacted with isocyanates of the formula (III) ##STR8## in whichR² to R⁷, n and Z have the abovementioned meanings, if appropriate inthe presence of a base and if appropriate in the presence of diluents orsolvents, or

(b) are reacted with halogenocarbonyl compounds of the formula (IV)##STR9## in which R¹ to R⁷, n and Z have the abovementioned meanings,and

Hal represents halogen, preferably chlorine,

if appropriate in the presence of an acid acceptor and if appropriate inthe presence of a solvent or diluent.

It has further been found that the substituted aminophenyl carbamates ofthe formula (I) have a good action against pests, above all a highfungicidal activity. The new compounds can also be used in synergisticmixtures together with other known, highly active compounds.

Surprisingly, the aminophenyl carbamates of the formula (I) according tothe invention exhibit, inter alia, a stronger fungicidal action thanknown compounds which are similar compounds with respect to their actionand/or chemically.

In the context of the present invention, the substituents generally havethe following meanings:

Halogen, everywhere where not otherwise stated, can denote fluorine,chlorine, bromine and iodine, preferably fluorine, chlorine and bromine.

Optionally substituted alkyl generally represents a straight-chain orbranched hydrocarbon radical having 1 to 20 carbon atoms, preferablyhaving 1 to 18 carbon atoms. Examples which may be mentioned are methyl,ethyl, n- and iso-propyl, n-, sec.-, iso- and tert.-butyl, hexyl,heptyl, dodeyl and octadecyl.

Substituents of an alkyl radical which may be mentioned as examples arehalogen, as defined above, in addition alkoxy and alkylthio.

Alkoxy and alkylthio and alkylsulfonyl generally have a straight-chainor branched hydrocarbon radical which has 1 to 6, preferably 1 to 4, andparticularly preferably 1 or 2, carbon atoms in the alkoxy or alkylthioor alkylsulfonyl part and which is bonded via oxygen, sulfur or SO₂respectively.

Examples of substituted alkyl radicals which may be mentioned are:fluoromethyl, chloromethyl, bromomethyl, fluoroethyl, chloroethyl,bromoethyl, fluoropropyl, chloropropyl, bromopropyl, fluorobutyl,chlorobutyl, bromobutyl, fluoroisopropyl, chloroisopropyl,bromoisopropyl, difluoromethyl, trifluoromethyl, dichloromethyl,trichloromethyl, difluoroethyl, dichloroethyl, trifluoroethyl,tetrafluoroethyl, difluorobutyl, dichlorobutyl, trichloroethyl andtrifluoropropyl. Very particularly preferred are trifluoromethyl,1-fluoro-2-fluoromethylprop-2-yl and 1-chloro-2-methyl-prop-2-yl.Furthermore methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl,methoxypentyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl,ethoxypentyl, propoxymethyl, propoxyethyl, propoxypropyl, propoxybutyl,propoxypentyl, butoxymethyl, butoxyethyl, butoxypropyl, butoxybutyl andbutoxypentyl. Particularly preferred is 2-methoxyprop-2-yl.

Furthermore methylthiomethyl, methylthioethyl, methylthiopropyl,methylthiobutyl, methylthiopentyl, ethylthiomethyl, ethylthioethyl,ethylthiopropyl, ethylthiobutyl, ethylthiopentyl, propylthiomethyl,propylthioethyl, propylthiopropyl, propylthiobutyl, propylthiopentyl,butylthiomethyl, butylthioethyl, butylthiopropyl, butylthiobutyl andbutylthiopentyl, methylsulfonyl, ethylsulfonyl and propylsulfonyl.

Alkyl, alkoxy and alkoxyalkyl represent a radical which has 1 to 6,preferably 1 to 4, carbon atoms per alkyl unit. Examples are shownhereinabove.

Halogenoalkoxy and halogenoalkylthio generally represent astraight-chain or branched hydrocarbon radical which has 1 to 6 carbonatoms and 1 to 9 identical or different halogen atoms and which isbonded via oxygen or sulfur respectively. Preferred radicals are thosehaving 1 to 4 carbon atoms and 1 to 5 identical or different halogenatoms. Very particularly preferred radicals are those having 1 or 2carbon atoms and 1 to 3 identical or different halogen atoms. Exampleswhich may be mentioned are trifluoromethoxy, trichloromethoxy,difluorochloromethoxy, dichlorofluoromethoxy, difluoroethoxy,trifluoroethoxy, tetrafluoroethoxy, pentafluoroethoxy,trifluoromethylthio, trichloromethylthio, difluorochloromethylthio,dichlorofluoromethylthio, difluoroethylthio, trifluoromethylthio andtetrafluorethylthio.

Halogenoalkyl corresponds in meaning to halogenoalkoxy.

Alkenyl generally represents a straight-chain or branched hydrocarbonradical having 2 to 16 carbon atoms and one or more, preferably one ortwo, double bonds. Lower alkenyl having 2 to 10 carbon atoms and onedouble bond is preferred. An alkenyl radical having 2 to 4 carbon atomsand one double bond is particularly preferred. Examples which may bementioned are vinyl, allyl, propenyl, isopropenyl, butenyl, isobutenyl,pentenyl, isopentenyl, hexenyl, isohexenyl, heptenyl, isoheptenyl,octenyl and isooctenyl.

Halogenoalkenyl generally represents straight-chain or branched alkylhaving 1 to 6 carbon atoms and one or more identical or differenthalogen atoms and having one or more double bonds. Preferred radicalsare those having 1 to 4 carbon atoms, 1 to 4 identical or differenthalogen atoms and one double bond. Examples which may be mentioned are2,2-dichlorovinyl and 1,2,2-trichlorovinyl.

Aryl can represent an aromatic hydrocarbon radical having 6 to 12 carbonatoms. Examples which may be mentioned are phenyl, naphthyl andbiphenyl. Phenyl is preferred.

Aralkyl can represent a radical having 7 to 18 carbon atoms, it beingpossible for a straight-chain or branched alkyl radical having 1 to 6,preferably 1 to 4, carbon atoms to be substituted by an aromatic radicalhaving 6 to 12, preferably 6, carbon atoms. Examples which may bementioned are benzyl, phenylethyl and phenylpropyl. Benzyl is preferred.

The aryl and aralkyl radicals may optionally be monosubstituted orpolysubstituted by identical or different substituents. Substituentswhich may be mentioned as examples are halogen, alkyl having 1 to 6carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having 1 to 6carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 9identical or different halogen atoms, halogenoalkoxy having 1 to 6carbon atoms and 1 to 9 identical or different halogen atoms,halogenoalkylthio having 1 to 6 carbon atoms and 1 to 9 identical ordifferent halogen atoms, cyano and nitro. These radicals have thepreferred and particularly preferred meaning as already described above.

Cycloalkyl generally represents a cyclic hydrocarbon radical having 3 to10 carbon atoms. The cyclopropyl, cyclopentyl and cyclohexyl radicalsare preferred. Examples which may be mentioned are cyclopropyl,cyclobutyl, cyclopentyl, cyclohexyl and cyclodecanyl.

Cycloalkyl-alkyl can represent a radical having 4 to 20 carbon atoms, itbeing possible for a straight-chain or branched alkyl radical having 1to 10 carbon atoms to be substituted by a cycloalkyl radical having 3 to10 carbon atoms. Examples which may be mentioned are cyclopropylmethyl,cyclopentylmethyl, cyclohexylmethyl, 1-cyclohexylethyl,2-cyclohexylethyl, cycloheptylmethyl and 2-cycloheptylethyl.

The cycloalkyl and cycloalkyl-alkyl radicals may be monosubstituted orpolysubstituted by identical or different substituents. Substituentswhich may be mentioned as examples are halogen, alkyl having 1 to 6carbon atoms and halogenoalkyl having 1 to 6 carbon atoms and 1 to 9identical or different halogen atoms. The substituents have thepreferred and particularly preferred meaning which has already beengiven further above for the radicals.

Cycloalkenyl can represent a cyclic hydrocarbon radical having 5 to 10carbon atoms and having one or more double bonds. Radicals having 5 to 6carbon atoms and one double bond are preferred. The cycloalkenyl radicalmay be monosubstituted or polysubstituted by identical or differentalkyl having 1 to 6 carbon atoms. The preferred and particularlypreferred definition of the alkyl radical corresponds to that which isgiven above.

Heterocyclic ring can represent a radical having 5 to 7 ring members,preferably having 5 or 6 ring members, one or more hetero atoms, such asoxygen, sulphur or nitrogen, being included in addition to carbon. 5- or6-membered rings having one or two oxygen atoms are preferred. Exampleswhich may be mentioned are oxolanyl, oxanyl, dioxolanyl and dioxanyl.The heterocyclic rings may be monosubstituted or polysubstituted byidentical or different alkyl having 1 to 6, preferably 1 to 4 andparticularly preferably 1 or 2, carbon atoms. Examples which may bementioned are: 2-methyl-oxolan-2-yl, 2-methyl-oxan-2-yl,5-methyl-1,3-dioxolan-5-yl, 2-ethyl-oxolan-2-yl, 2-ethyl-oxan-2-yl and5-ethyl-1,3-dioxolan-5-yl.

Formula (I) provides a general definition of the substituted aminophenylcarbamates according to the invention. Preferred compounds of theformula (I) are those

in which

X represents --CO--NR⁸ R⁹ ; --CO--OR⁹ ; --CO--SR⁹ ; --CO--R¹⁰ ; --SO₂ R⁹or hydrogen, in which

R⁸ represents hydrogen or straight-chain or branched alkyl having 1 to 6carbon atoms,

R⁹ represents aryl having 6 to 12 carbon atoms, aryl having 6 to 12carbon atoms which is monosubstituted to hexasubstituted by identical ordifferent substituents from the series comprising halogen, alkyl having1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms and 1 to 9identical or different halogen atoms, halogenoalkoxy having 1 to 6carbon atoms and 1 to 9 identical or different halogen atoms,halogenoalkylthio having 1 to 6 carbon atoms and 1 to 9 identical ordifferent halogen atoms, cyano and nitro; furthermore represents aralkylhaving 6 to 12 carbon atoms in the aryl part and having 1 to 6 carbonatoms in the straight-chain or branched alkyl part, it being possiblefor the aryl radical to be monosubstituted to hexasubstituted byidentical or different substituents from the series comprising theabovementioned aryl substituents; furthermore represents straight-chainor branched alkyl having 1 to 20 carbon atoms; furthermore representsalkyl having 1 to 20 carbon atoms which is monosubstituted totetrasubstituted by identical or different substituents from the seriescomprising halogen, alkoxy having 1 to 6 carbon atoms and alkylthiohaving 1 to 6 carbon atoms, it being possible for each of the alkylparts to be straight-chain or branched; in addition representsstraight-chain or branched alkenyl having 2 to 16 carbon atoms oralkenyl having 2 to 6 carbon atoms which is monosubstituted tohexasubstituted by identical or different halogen; in additionrepresents cycloalkyl having 3 to 10 carbon atoms or cycloalkylalkylhaving 1 to 10 carbon atoms in the straight-chain or branched alkyl partand 3 to 10 carbon atoms in the cycloalkyl part, it being possible forthe cyclic parts, in each case independently, to be monosubstituted tohexasubstituted by identical or different substituents from the seriescomprising halogen, straight-chain or branched alkyl having 1 to 6carbon atoms and halogenoalkyl having 1 to 6 carbon atoms and 1 to 9identical or different halogen atoms, or R⁹, in addition, representscycloalkenyl which has 5 to 10 carbon atoms and which may bemonosubstituted to hexasubstituted by identical or different,straight-chain or branched alkyl having 1 to 6 carbon atoms;

R¹⁰ has the meaning of R⁹ or represents a heterocyclic ring having 5 to7 ring members, one or more hetero atoms being included in addition tocarbon. The heterocyclic ring may be monosubstituted to hexasubstitutedby identical or different, straight-chain or branched alkyl having 1 to6 carbon atoms;

Y¹ to Y⁴ are identical or different and represent hydrogen, halogen,nitro, cyano, straight-chain or branched alkyl having 1 to 6 carbonatoms, halogenoalkyl having 1 to 6 carbon atoms in the straight-chain orbranched alkyl part and 1 to 9 identical or different halogen atoms,alkoxy, halogenoalkoxy, alkylthio, alkylsulfonyl or halogenoalkylthio ineach case having 1 to 6 carbon atoms in the straight-chain or branchedalkyl part and, if appropriate, 1 to 9 identical or different halogenatoms;

R¹ to R⁷ are identical or different and represent hydrogen,straight-chain or branched alkyl having 1 to 6 carbon atoms,halogenoalkyl having 1 to 6 carbon atoms in the straight-chain orbranched alkyl part and 1 to 9 identical or different halogen atoms, oralkoxyalkyl having 1 to 6 carbon atoms in each straight-chain orbranched alkyl part;

n represents 0 or 1, and

Z represents straight-chain or branched alkyl or halogenoalkyl eachhaving 1 to 6 carbon atoms and, if appropriate, 1 to 9 identical ordifferent halogen atoms, or the ##STR10## radical, in which R¹¹ to R¹⁴are identical or different and represent hydrogen, straight-chain orbranched alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6carbon atoms in the straight-chain or branched alkyl part and 1 to 9identical or different halogen atoms, or alkoxyalkyl having 1 to 6carbon atoms in each straight-chain or branched alkyl part, and

R¹⁵ represents straight-chain or branched alkyl, alkoxyalkyl orhalogenoalkyl each having 1 to 6 carbon atoms in each alkyl part and, ifappropriate, 1 to 9 identical or different halogen atoms.

Particularly preferred compounds of the formula (I) are those in which

X represents --CO--NR⁸ R⁹ ; --CO--OR⁹ ; --CO--R¹⁰ ; --SO₂ R⁹ orhydrogen, in which

R⁸ represents hydrogen,

R⁹ represents phenyl, benzyl, phenylethyl or 1-phenyl-1-methylethyl eachof which is optionally monosubstituted, disubstituted or trisubstitutedin the phenyl part by identical or different substituents from theseries comprising halogen, straight-chain or branched alkyl having 1 to4 carbon atoms, straight-chain or branched alkoxy having 1 to 4 carbonatoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms,halogenoalkyl, halogenoalkoxy or halogenoalkylthio in each case having 1to 4 carbon atoms in the straight-chain or branched alkyl part and 1 to5 identical or different halogen atoms, cyano or nitro; representsstraight-chain or branched alkyl having 1 to 18 carbon atoms; alkylwhich has 1 to 4 carbon atoms in the straight-chain or branched alkoxyor alkylthio part and 1 to 10 carbon atoms in the alkyl part and whichis monosubstituted, disubstituted or trisubstituted by identical ordifferent substituents from the series comprising halogen, alkoxy oralkylthio; straight-chain or branched alkenyl having 2 to 8 carbonatoms; straight-chain or branched alkenyl having 2 to 4 carbon atomswhich is monosubstituted, disubstituted or trisubstituted by identicalor different halogen; cycloalkyl which has 3 to 6 carbon atoms orcycloalkyl-alkyl which has 3 to 6 carbon atoms in the cycloalkyl partand 1 to 6 carbon atoms in the straight-chain or branched alkyl part andeach of which is optionally monosubstituted, disubstituted ortrisubstituted by identical or different substituents from the seriescomprising halogen, straight-chain or branched alkyl having 1 to 4carbon atoms or straight-chain or branched halogenoalkyl having 1 to 4carbon atoms and 1 to 5 identical or different halogen atoms;

R¹⁰ has the meaning of R⁹ or represents a 5-or 6-membered heterocyclicring which contains one or two oxygen atoms and which is optionallymonosubstituted, disubstituted or trisubstituted by straight-chain orbranched alkyl having 1 to 4 carbon atoms,

Y¹ to Y⁴ are identical or different and represent hydrogen, halogen,straight-chain or branched alkyl having 1 to 4 carbon atoms,straight-chain or branched alkoxy or alkylsulfonyl having 1 to 4 carbonatoms in each alkyl part, or halogenoalkyl having 1 to 4 carbon atoms inthe straight-chain or branched alkyl part and 1 to 5 identical ordifferent halogen atoms;

R¹ to R⁷ are identical or different and represent hydrogen orstraight-chain or branched alkyl having 1 to 6 carbon atoms,

n represents 0, and

Z represents straight-chain or branched alkyl or halogenoalkyl eachhaving 1 to 4 carbon atoms and, if appropriate, 1 to 5 identical ordifferent halogen atoms, or the ##STR11## radical, in which R¹¹ to R¹⁴are identical or different and represent hydrogen, straight-chain orbranched alkyl or halogenoalkyl in each case having 1 to 4 carbon atomsand, if appropriate, 1 to 5 identical or different halogen atoms and

R¹⁵ represents straight-chain or branched alkyl, alkoxyalkyl orhalogenoalkyl in each case having 1 to 4 carbon atoms in each alkyl partand, if appropriate, 1 to 5 identical or different halogen atoms.

Very particularly preferred compounds of the formula (I) are those inwhich

X represents --CO--NHR⁹ ; --CO--OR⁹ ; --CO--R¹⁰ or --SO₂ R⁹, in which

R⁹ represents phenyl which is optionally monosubstituted, disubstitutedor trisubstituted by identical or different substituents from the seriescomprising methyl, ethyl, methoxy, ethoxy, trichloromethyl,trifluoromethyl, trichloromethoxy, trifluoromethoxy, fluorine andchlorine; represents benzyl; straight-chain or branched alkyl having 1to 5 carbon atoms; halogenoalkyl having 1 to 4 carbon atoms and 1 or 2chlorine or fluorine atoms; halogenoalkenyl having 2 or 3 carbon atomsand 1 to 4 chlorine atoms; cyclopropyl or cyclohexyl each of which isoptionally monosubstituted, disubstituted or trisubstituted by identicalor different, straight-chain or branched alkyl having 1 to 4 carbonatoms,

R¹⁰ represents straight-chain or branched alkyl having 1 to 18 carbonatoms, represents phenyl, cyclopropyl or cyclohexyl each of which isoptionally monosubstituted, disubstituted or trisubstituted by identicalor different substituents from the series comprising methyl, ethyl,n-propyl, iso-propyl, chlorine or trifluoromethyl; phenylalkyl which has1 to 3 carbon atoms in the straight-chain or branched alkyl part andwhich is optionally monosubstituted or disubstituted by chlorine;straight-chain or branched halogenoalkyl having 1 to 4 carbon atoms and1 or 2 chlorine or fluorine atoms; straight-chain or branchedhalogenoalkenyl having 2 to 4 carbon atoms and 1 to 4 identical ordifferent halogen atoms, such as chlorine and fluorine, or oxanyl oroxolanyl or dioxanyl or dioxolanyl each of which is optionallymonosubstituted by methyl or ethyl;

Y¹ to Y⁴ are identical or different and represent hydrogen, chlorine,fluorine, bromine, methyl or trifluoromethyl,

R¹ to R⁷ are identical or different and represent hydrogen or methyl,

n represents 0, and

Z represents straight-chain or branched alkyl having 1 to 4 carbonatoms, or the ##STR12## radical, in which R¹¹ to R¹⁴ represent hydrogen,and

R¹⁵ represents methyl, ethyl, propyl, butyl methoxyethyl or ethoxyethyl.

In the compounds the amino group is in the 2-, 3- or 4-position,particularly preferably in the 3- or 4-position and very particularlypreferably in 4-position to the carbamate radical.

If, for example, 2,6-dichloro-4-(tert.-butylcarbonylamino)-phenol and2-methoxyethyl isocyanate are used as starting materials, the course ofthe reaction of process variant (a) can be illustrated by the followingequation: ##STR13##

If, for example, 2,6-dichloro-4-(methyl-carbonylamino)-phenol andN-methyl-N-(3,6-dioxapheptyl)-carbamoyl chloride are used as startingmaterials, the course of the reaction of process variant (b) may beillustrated by the following equation: ##STR14##

Formula (II) provides a general definition of the aminophenols requiredas starting materials for carrying out process variants (a) and (b)according to the invention. In this formula (II), the X and Y¹ to Y⁴radicals have the meanings which have already been given in connectionwith the description of the compounds of the formula (I) according tothe invention. The majority of the compounds are known and can beprepared by analogous processes [cf. "Methoden der organischen Chemie"[Methods of organic chemistry] Houben-Weyl, Vol. VI/1C Phenols, Part 1,Georg Thieme Verlag Stuttgart (1976)].

Thus, for example, 4-amino-2-trifluoromethylphenyl is known from J. Org.Chem. 27, 4660 (1962); 4-amino-2-chloro- or-2-bromo-6-trifluoromethylphenols are known from Japanese PreliminaryPublished Specification Jp 61/126055, and, for example,4-amino-2,3,5,6-tetrafluorophenol is known from Zh. Org. Khim. 10(9),1923-1927 (1974). The compounds of the formula (IIA) or (IIB) ##STR15##in which Y⁵ represents fluorine or chlorine, which are still new, forexample, can be prepared, for example, from appropriate hydroxybenzoicacids of the formula (VA) or (VB) respectively ##STR16## bydecarboxylation, and the resultant phenols of the formulae (VIA) or(VIB) respectively ##STR17## are nitrated to give the nitro compounds ofthe formula (VIIA) or (VIIB) respectively ##STR18## which are thenhydrogenated, for example using hydrogen and Raney nickel, to give thecorresponding amines of the formulae (IIA) and (IIB).

The compounds of the formulae (VIIA) and (VIIB) are also compoundsaccording to the invention.

Formula (III) provides a general definition of the isocyanates which areadditionally required for carrying out process variant (a) according tothe invention. In this formula (III), the radicals R² to R⁷, n and Zhave the meanings which have already been given in connection with thedescription of the compounds of the formula (I) according to theinvention. The compounds are known and can be prepared by analogousprocesses [cf. "Methoden der organischen Chemie" [Methods of organicchemistry] Houben-Weyl, Vol. E4, Carbonic acid derivatives, Georg ThiemeVerlag Stuttgart, New York, pp. 738 ff (1983)].

The formula (IV) provides a general definition of the halogenocarbonylcompounds furthermore required for carrying out process variant (b)according to the invention. In this formula (IV), the radicals Hal, R¹to R⁷, n and Z have the meanings which have already been given inconnection with the description of the compounds of the formula (I)according to the invention.

The majority of the compounds of the formula (IV) are known or can beprepared by analogous processes [cf. "Methoden der organischen Chemie"[Methods of organic chemistry] Houben-Weyl, Vol. E4, Carbonic acidderivatives, Georg Thieme Verlag Stuttgart, New York, pp. 36 ff (1983)].

Suitable diluents for carrying out process variants (a) and (b)according to the invention are virtually all inert organic diluents.These include, in particular, aliphatic and aromatic, optionallyhalogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane,petroleum ether, benzine, ligroin, benzene, toluene, xylene, methylenechloride, ethylene chloride, chloroform, carbon tetrachloride,chlorobenzene and o-dichlorobenzene, ethers, such as diethyl and dibutylether, glycol dimethyl ether and diglycol dimethyl ether,tetrahydrofuran and dioxane, ketones, such as acetone, methyl ethyl,methyl isopropyl and methyl isobutyl ketone, esters, such as methylacetate and ethyl acetate, nitriles, such as, for example, acetonitrileand propionitrile, amides, such as, for example, dimethylformamide,dimethylacetamide and N-methylpyrrolidone, and also dimethyl sulphoxide,tetramethylene sulphone and hexamethylphosphoric triamide.

Process variants (a) and (b) according to the invention are generallycarried out at temperatures between -50° C. and 120° C. The rangebetween 0° C. and 110° C. is preferred. The reactions are generallycarried out at atmospheric pressure.

Process variant (b) is carried out, if appropriate, in the presence ofacid acceptors. Acid acceptors which can be used are all conventionalacid-binding agents. Alkali metal carbonates and alkali metalalcoholates, such as sodium carbonate, potassium carbonate, sodiummethylate and ethylate, potassium methylate and ethylate, furthermorealiphatic, aromatic or heterocyclic amines, for example triethylamine,trimethylamine, dimethylaniline, 1,8-diazabicyclo(5,4,0)-undec-7ene,dimethylbenzylamine and pyridine, have proved particularly successful.

Process variant (a) is carried out, if appropriate, in the presence of abase. All bases which are cited as acid acceptors can be used.

To carry out process variant (a) according to the invention, 1 to 2mols, in particular 1 to 1.4 mols, of the compounds of the generalformula (III) are preferably employed per mol of the phenol of thegeneral formula (II).

To carry out process variant (b) according to the invention, 1 to 2mols, in particular 1 to 1 to 4 mols, of the compounds of the formula(IV) are preferably employed per mol of phenol of the general formula(II).

Work-up takes place by conventional methods, for example throughextraction of the products from the water-diluted reaction mixture usingtoluene or methylene chloride, washing the organic phase with water,drying the organic phase, and distillation or so-called "incipientdistillation" of the product, i.e. relatively lengthy heating tomoderately elevated temperatures under reduced pressure in order to freethe product of the final volatile components, or through chromatographicpurification on silica gel or through crystallization. The refractiveindex, melting point, R_(f) value or boiling point are used tocharacterize the compounds.

The active compounds according to the invention have a strong actionagainst pests and can be employed in practice for combating undesiredharmful organisms. The active compounds are suitable for use, inparticular, as fungicides.

Fungicidal agents in plant protection are employed, for example, forcombating Plasmodiophoromycetes, Oomycetes, Chytridiomycetes,Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes.

Bacteriicidal agents are employed in plant protection, for example forcombating Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae,Corynebacteriazeae and Streptomycetaceae.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as example, butnot by way of limitation: Xanthomonas species, such as, for example,Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, forexample, Pseudomonas syringae pv. Lachrymans; Erwinia species, such as,for example, Erwinia amylovora; Pythium species, such as, for example,Pythium ultimum; Phyto-phthora species, such as, for example,Phytophthora infes-tans; Pseudoperonospora species, such as, forexample, Pseudoperonospora humuli or Pseudoperonospora cubensis;Plasmopara species, such as, for example, Plasmopara viti-cola;Peronospora species, such as, for example, Perono-spora pisi or P.brassicae; Erysiphe species, such as, for example, Erysiphe graminis;Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;Podosphaera species, such as, for example, Podosphaera Leucotricha;Venturia species, such as, for example, Venturia inaequalis; Pyrenophoraspecies, such as, for example, Pyrenophora teres or P. graminea (conidiaform: Dreschslera, syn: Helminthosporium); Cochliobolus species, suchas, for example, Cochliobolus sativus (conidia form: Drechslera, syn:Helminthosporium); Uromyces species, such as, for example, Uromycesappendiculatus; Puccinia species, such as, for example, Pucciniarecondita; Tilletia species, such as, for example, Tilletia caries;Ustilago species, such as, for example, Ustilago nuda or Ustilagoavenae; Pellicularia species, such as, for example, Pelliculariasasakii; Pyricularia species, such as, for example, Pyricularia oryzae;Fusarium species, such as, for example, Fusarium culmorum; Botrytisspecies, such as, for example, Botrytis cinerea; Septoria species, suchas, for example, Septoria nodorum; Leptosphaeria species, such as, forexample, Leptosphaeria nodorum; Cercospora species, such as, forexample, Cercospora canescens; Alternaria species, such as, for example,Alternaria brassicae and Pseudocercosporella species, such as, forexample, Pseudocercosporella herpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds can be converted to the customary formulation, suchas solutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols, very fine capsules in polymeric substances and in coatingcompositions for seed, as well as ULV formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable: for exmaple non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for examfple alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalines and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seeds of the plants can also betreated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02%, are required at the place ofaction.

PREPARATION EXAMPLES EXAMPLE 1 ##STR19##

10 g (0.038 mol) of 2-chloro-4-(tert.-butyl-carbonylamino)-phenol aredissolved in 20 ml of toluene, and 4.2 g (0.042 mol) of 2-methoxyethylisocyanate are added. 30 mg (0.2 mmol) of1,8-diazabicyclo-(5,4,0)-undec-7-ene are subsequently added to thewell-stirred reaction mixture. When the exothermic reaction (to 45° C.)has subsided, the mixture is stirred for a further 2 hours at 20° C. andcooled to 0° C., and the precipitated solid is filtered off undersuction. The solid is subsequently taken up agin in toluene: acetone=7:3and filtered through silica gel using the same eluent. After evaporationof the solvents, 11.2 g (90% of theory) of2-chloro-4-(tert.-butylcarbonylamino)-phenyl 2-methoxyethylcarbamate ofmelting point 118° C. are obtained.

The following are prepared analogously:

                                      TABLE 1                                     __________________________________________________________________________     ##STR20##                                                                     Example No.                                                                        X             Y.sup.1                                                                         Y.sup.2                                                                          Y.sup.3                                                                          Y.sup.4                                                                         R.sup.1                                                                          ##STR21##        Physical data: *R.sub.f                                                       value: silica gel                                                             60F254; (Merck) eluent;                                                       oluene:acetone = 7:3;                                                         refractive index                                                              n.sub.D.sup.20 ;                                                              melting point               __________________________________________________________________________                                                      °C.                   2   COC.sub.4 H.sub.9 -tert.                                                                    H Cl Cl H H   CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                         OCH.sub.3         100                          3   COC.sub.4 H.sub.9 -tert.                                                                    H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         67-73                        4   COC.sub.4 H.sub.9 -tert.                                                                    Cl                                                                              H  H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.45*                        5   COOC.sub.2 H.sub.5                                                                          H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.5290                       6   COOC.sub.4 H.sub.9 -sek.                                                                    H H  H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         54-55                        7   COOC.sub.3 H.sub.7 -i                                                                       H CH.sub.3                                                                         H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         74-76                        8   COOC.sub.2 H.sub.5                                                                          H CH.sub.3                                                                         H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         57-58                        9   COOC.sub.2 H.sub.5                                                                          H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.529                       10   COOC.sub.3 H.sub.7 -i                                                                       H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.527                       11                                                                                  ##STR22##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         76-80                       12   H             H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.36*                       13   CONHCH.sub.2C(CH.sub.3).sub.3                                                               H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         129-131                     14                                                                                  ##STR23##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         136-139                     15   CONHCH.sub.3  H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         190-191                     16                                                                                  ##STR24##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         176                         17                                                                                  ##STR25##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.44*                       18   COCH.sub.3    H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.532                       19   COCH.sub.3    H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         128                         20                                                                                  ##STR26##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.47*                       21   COC.sub.4 H.sub.9 -tert.                                                                    H Br CF.sub.3                                                                         H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.53*                       22   COC.sub.4 H.sub.9 -tert.                                                                    H CF.sub.3                                                                         H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.39*                       23   COC.sub.4 H.sub.9 -tert.                                                                    Cl                                                                              Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         63-65                       24   CO(CH.sub.2).sub.16 CH.sub.3                                                                H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         47                          25                                                                                  ##STR27##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         62-64                       26                                                                                  ##STR28##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         66-67                       27                                                                                  ##STR29##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         87-89                       28                                                                                  ##STR30##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         80-82                       29                                                                                  ##STR31##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         72-75                       30                                                                                  ##STR32##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.56*                       31                                                                                  ##STR33##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         0.57*                       32                                                                                  ##STR34##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.516                       33   COOC.sub.3 H.sub.7 -i                                                                       Cl                                                                              Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         98                          34   COOC.sub.2 H.sub.5                                                                          Cl                                                                              Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         95                          35   COC.sub.4 H.sub.9 -tert.                                                                    Cl                                                                              Cl H  H CH.sub.3                                                                         CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.5265                      36                                                                                  ##STR35##    H Cl Cl H H  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                            136                         37                                                                                  ##STR36##    H Cl Cl H H  CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.4                                           H.sub.9 -n        105                         38                                                                                  ##STR37##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OC.sub.4 H.sub.9 -n                                                                             84                          39   COOC.sub.4 H.sub.9 -i                                                                       Cl                                                                              H  H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.5186                      40                                                                                  ##STR38##    H Cl Cl H H  CH.sub.2 CH.sub.2 CH.sub.2 OC.sub.2                                           H.sub.5           138-141                     41                                                                                  ##STR39##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     130                         42   COOC.sub.2 H.sub.5                                                                          Cl                                                                              H  H  H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.3         1.5328                      43                                                                                  ##STR40##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     79                          44                                                                                  ##STR41##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     129-132                     45                                                                                  ##STR42##    H CF.sub.3                                                                         Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     114                         46   COC.sub.4 H.sub.9 -tert.                                                                    Cl                                                                              Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     68-69                       47                                                                                  ##STR43##    H H  Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     122                         48                                                                                  ##STR44##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     135                         49                                                                                  ##STR45##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     106-109                     50                                                                                  ##STR46##    F Cl Cl F H  CH.sub.2 CH.sub.2 OCH.sub.3                   51                                                                                  ##STR47##    H Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     100                         52                                                                                  ##STR48##    H Cl H  H H  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                  88                          53                                                                                  ##STR49##    Cl                                                                              Cl H  H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     1.5430                      54                                                                                  ##STR50##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     156                         55                                                                                  ##STR51##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     115                         56                                                                                  ##STR52##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     102                         57                                                                                  ##STR53##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     80                          58                                                                                  ##STR54##    F F  Cl F H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     148                         59                                                                                  ##STR55##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OC.sub.3 H.sub.7                                                           96                          60                                                                                  ##STR56##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OC.sub.4 H.sub.9                                                           76                          61                                                                                  ##STR57##    H Cl Cl H H  CH(C.sub.2 H.sub.5)CH.sub.2 OCH.sub.3                                                           108                         62                                                                                  ##STR58##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OCH(CH.sub.3)C.sub.2                                     H.sub.5           108                         63                                                                                  ##STR59##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     85                          64                                                                                  ##STR60##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OC.sub.3 H.sub.7                                                           110                         65                                                                                  ##STR61##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OC.sub.2 H.sub.5                                                           107                         66                                                                                  ##STR62##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                  83                          67                                                                                  ##STR63##    H CH.sub.3                                                                         H  H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     115                         68                                                                                  ##STR64##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2                                          OCH.sub.2 CH.sub.2 OCH.sub.3                                                                    61                          69                                                                                  ##STR65##    H Cl H  H H  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                  88                          70                                                                                  ##STR66##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     103                         71                                                                                  ##STR67##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OCH.sub.2 C(CH.sub.3)                                    .sub.3            114                         72                                                                                  ##STR68##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     102                         73                                                                                  ##STR69##    H Cl Cl H H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                     71                          74                                                                                  ##STR70##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                  50                          75                                                                                  ##STR71##    H Cl Cl H H  CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                                  61                          76                                                                                  ##STR72##    H Cl Cl H H  CH.sub.2 C(CH.sub.3).sub.2 OCH.sub.3                                                            129                         77                                                                                  ##STR73##    H Cl H  H H  CH.sub.2 C(CH.sub.3).sub.2 OCH.sub.3          78                                                                                  ##STR74##    H Cl Cl H H  C(CH.sub.3).sub.2 CH.sub.2 OCH.sub.3          79                                                                                  ##STR75##    H Cl H  H H  C(CH.sub.3).sub. 2 CH.sub.2 OCH.sub.3         80                                                                                  ##STR76##    H Cl Cl H H                                                                                 ##STR77##                                    __________________________________________________________________________

                                      TABLE 2                                     __________________________________________________________________________     ##STR78##                                                                     Example No.                                                                          X       Y.sup.1                                                                         Y.sup.2                                                                         Y.sup.3                                                                          Y.sup.4                                                                         R.sup.1                                                                         ##STR79##    melting point °C.refractive                                            index n.sub.D.sup.20 ;eluent;                                                toluene:acetone = 7:3;silica gel                                              60F254; (Merck);Physical data:                                                *R.sub.f value:                        __________________________________________________________________________    81                                                                                    ##STR80##                                                                            F H Cl H H CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                             1.5322                                 82                                                                                    ##STR81##                                                                            F H CH.sub.3                                                                         H H CH(C.sub.2 H.sub.5)CH.sub.2 OCH.sub.3                                                      70                                     83                                                                                    ##STR82##                                                                            F H CH.sub.3                                                                         H H CH.sub.2 CH.sub.2 OCH.sub.3                                                                102                                    84                                                                                    ##STR83##                                                                            F H Cl H H CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                             85                                     85                                                                                    ##STR84##                                                                            F H Cl H H CH.sub.2 CH.sub.2 OCH.sub.3                                                                110                                    86                                                                                    ##STR85##                                                                            F H Cl H H CH.sub.2 CH.sub.2 OCH.sub.3                                                                97                                     __________________________________________________________________________

                                      TABLE 3                                     __________________________________________________________________________     ##STR86##                                                                     Example No.                                                                          X       Y.sup.1                                                                         Y.sup.2                                                                            Y.sup.3                                                                         Y.sup.4                                                                         R.sup.1                                                                         ##STR87##   melting point °C.refractiv                                            e index n.sub.D.sup.20 ;eluent;                                               toluene:acetone = 7:3;silica gel                                              60F254; (Merck);Physical data:                                                *R.sub.f value:                       __________________________________________________________________________    87                                                                                    ##STR88##                                                                            H Cl   H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               94                                    88                                                                                    ##STR89##                                                                            H H    H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               101                                   89                                                                                    ##STR90##                                                                            H Cl   H Cl                                                                              H CH.sub.2 CH.sub.2 OCH.sub.3                                                               146                                   90     COC(CH.sub.3).sub.3                                                                   H C(CH.sub.3).sub.3                                                                  H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               132                                   91     COC(CH.sub.3).sub.3                                                                   H F    H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               104                                   92     COC(CH.sub.3).sub.3                                                                   H SO.sub.2 CH.sub.3                                                                  H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               *0.35                                 93                                                                                    ##STR91##                                                                            H Cl   H H H CH.sub.2 CH.sub.2 OCH.sub.3                                                               101                                   __________________________________________________________________________

PREPARATION OF THE STARTING MATERIALS OF THE FORMULA (III) EXAMPLEIII 1. 2-Methoxy-ethyl isocyanate

1.1 Preparation of 2-ethylhexyl N-(2-methoxyethyl)-carbamate(corresponding to European Patent Specification No. 0,027,940)

225 g (3.0 mols) of 2-methoxyethylamine, 180 g (3.0 mols) of urea, 1,950g (15 mols) of 2-ethylhexanol and 3 g of dibutyltin oxide are introducedinto a 4 liter round-bottom flask equipped with reflux condenser, andthe mixture is heated while stirring. A vigorous evolution of ammoniasets in at temperatures above 110° C. Ammonia gas is remvoed through thereflux condenser and absorbed in water. Over the course of 3 hours, thetemperature is increased to 180° C. (reflux), the elimination of ammoniavirtually ceasing. After a further 2 hours under reflux, the mixture isfreed of remaining ammonia by flushing with nitrogen and subsequentlysubjected to fractional distillation. After a first cut comprisingmainly ethylhexanol, the desired urethane distills over at 98°-100°C./0.1 mbar as a colorless liquid (yield: 617 g=89% of theory). 27 g ofa brown liquid remain as the distillation residue and solidify to give apasty product on cooling.

1.2 Thermal cleavage of 2-ethylhexyl N-(2-methoxyethyl)-carbamate(corresponding to EP No. (0,054,817)

The cleavage apparatus used is a round-bottom flask which is fitted witha dropping funnel and a stirrer and to which two reflux condensers,which are subjected to thermostatic control by means of heat-transferoil, are attached one on top of the other. A withdrawal tray is locatedbetween the two reflux condensers.

the urethane is cleaved continuously without removing the residue.

pressure: 29 mbar

temperature: cleavage flask: 174°-178° C.

oil first cut of lower condenser: 135° C.

oil first cut of upper condenser: 65° C.

average residence time: about 4 hours

cleavage fractions:

withdrawal tray: 70.1% by weight of ethylhexanol

top of the upper condenser: 92.5% by weight of isocyanate

When the cleavage is complete, the mixtures obtained are in each casesubjected to fractional distillation.

Overall result of the cleavage:

urethane:

employed: 3.11 kg

recovered: 0.84 kg

reacted: 2.27 kg

2-methoxyethyl isocyanate, distilled: 920 g

(b.p. 124° C.), purity: 99.3% (GC)

→ selectivity: 92%

2-ethylhexanol: 1.23 kg

→ selectivity: 96%

residue: 114 g

PREPARATION OF THE STARTING MATERIALS FOR THE PREPARATION OF THECOMPOUNDS OF THE FORMULA (II), AND COMPOUNDS OF THE FORMULA (II) EXAMPLEA1: 3,5-Dichloro-2,6-difluoro-4-hydroxybenzoic acid

300 g of potassium hydroxide, 600 ml of water, 15 g oftetrabutylammonium chloride and 135 g of3,5-dichloro-2,4,6-trifluorobenzotrifluoride are introduced into astirred apparatus and the mixture is then refluxed for 5 hours. When thereaction is complete, the mixture is cooled and acidified by dropwiseaddition of hydrochloric acid. The solid porduct is filtered off undersuction and dried in vacuo. Yield: 93 g having a melting point of102°-5° C.

EXAMPLE A2: 3-Chloro-2,5,6-trifluoro-4-hydroxy-benzonic acid

From 400 g of NaOH, 1,200 ml of water, 15 g of tetraethylammoniumchloride and 276 g of 3-chloro-tetra-fluorobenzotrifluoride, 238 g ofproduct of melting point 87°-90° C. are obtained analogously to ExampleA1 on refluxing for 6 hours.

EXAMPLE A3: 2,6-Dichloro-3,5-difluorophenol

50 g of 3,5-dichloro-2,6-difluoro-4-hydroxy-benzoic acid and 10 ml ofdimethylformamide are mixed and heated. At 105°-130° C., carbon dioxideevolves, and the reaction is allowed to run to completion at thistemperature. 200 ml of toluene and then 80 ml of water are subsequentlystirred into the mixture, the phases are separated, and the organicphase is dried and subsequently distilled. 34 g product of boiling point87°-8° C. are obtained; n_(D) ²⁰ : 1.5310.

EXAMPLE A4:

2-Chloro-3,5,6-trifluorophenol of boiling point 68°-70° C./20 mbar areobtained analogously to Example A3.

EXAMPLE A5: 2,6-Dichloro-3,5-difluoro-4-nitro-phenol

20 g of 2,6-dichloro-3,5-difluorophenol are introduced into 70 ml ofacetic acid, and 8 g of 98% strength nitric acid are added dropwise. Themixture is subsequently stirred for a further 2 hours at roomtemperature and taken up in 150 ml of dichloromethane, and the solutionis washed twice with water. After removing the dichloromethane bydistillation, 18 g of product remain. 94% purity according to GCanalysis. EXAMPLE A6: 2-Chloro-3,5,6-trifluoro-4-nitrophenol

25 g of 2-chloro-3,5,6-trifluoro-4-nitrophenol of purity 93% and meltingpoint 107°-109° C. are obtained from 28 g of2-chloro-3,5,6-trifluoroephenol by nitration analogously to Example A5.

EXAMPLE A7: 2,6-Dichloro-3,5-difluoro-4-amino-phenol

18 g of 2,6-dichloro-3,5-difluoro-4-nitrophenol are hydrogenated in 100ml of methanol in the presence of 1.5 g of Raney nickel at 25°-45° C.using 30-50 bar of hydrogen until the take-up of hydrogen is complete.After filtration, the solution is freed from solvent under recucedpressure. 13 g of aminophenol (GC purity 98.4%) remain; m.p. 151° C.

EXAMPLE A8: 2-Chloro-3,5,6-trifluoro-4-amino-phenol

From 25 g of 2-chloro-3,5,6-trifluoro-4-nitrophenol in 120 ml ofmethanol and 2 g of Raney nickel, 20 g of aminophenol (GC purity 97%)are obtained by hydrogenation analogously to Example A7.

EXAMPLE A9: (2,4-Difluoro-5-nitro)-phenyl trifluorochloroethyl ether

150 g of potassium fluoride in 350 ml of tetramethylene sulphone areinitially introduced and dried azeotropically using xylene. 200 g of(2,4-dichloro-5-nitro)-phenyl trifluorochloroethyl ether are then added,and the mixture is heated at 180° C. for 5 hours, and subsequently at190°-195° C. for a further 5 hours with exclusion of moisture. Aftercooling, the batch is stirred into 1 liter of water and extractedrepeatedly with toluene. The toluene phase is washed twice with waterand then dried. 89 g of (2,4-Difluoro-5-nitor)-phenyltrifluorochloroethyl ether of boiling point 133°-37° C./16 mbar areobtained by distillation.

EXAMPLE A10: 2,4-difluoro-5-nitrophenol

50 g of (2,4-difluoro-5-nitro)-phenyl trifluorochloro-ethyl ether and 25ml of tetramethylene sulphone are initially introduced, and 50 ml ofconcentrated sulphuric acid and 0.5 g of iron(III) chloride are added.The mixture is then heated at 100° C. for 3 hours, and cooled, and 100 gof ice are added in order to subsequently reflux for a further 2 hours.After 250 ml of water had been stirred in, the product was extractedrepeatedly with toluene, and the toluene phase was dried and distilled.24 g of 2,4-difluoro-5-nitrophenol are obtained.

Boiling point: 160°-2° C./24 mbar, m.p. 117°-19° C.

EXAMPLE A11: 2,4-difluoro-5-amino-phenol

24 g of 2,4-Difluoro-5-nitrophenol, dissolved in 120 ml of methanol, aresubjected to hydrogenation at a hydrogen pressure of 20-40 bar at25°-45° C. in the presence of 2 g of Raney nickel. When constantpressure is reached (i.e. when the take-up of hydrogen is complete), thepressure is released and the mixture is cooled, the solution is freefrom catalyst by filtration, and the methanol is subsequently removed bydistillation at reduced pressure. 18 g (GC purity 97.5%) of2,4-difluoro-5-amino-phenol are obtained.

EXAMPLE A

Botrytis test (bean)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protection activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, 2 small pieces of agar covered with Botrytiscinerea are placed on each leaf. The inoculated plants are placed in adarkened humid chamber at 20° C. 3 days after the inoculation, the sizeof the infected spots on the leaves is evaluated.

The compounds of preparation Examples 39 and 42, for example, show at 50ppm an infection degree of 5%.

EXAMPLE B

Pyricularia test (rice)/protective

Solvent: 12.5 parts by weight of acetone

Emulsifier: 0.3 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, and theconcentrate is diluted with water and the stated amount of emulsifier,to the desired concentration.

To test for protective activity, young rice plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Pyricularia oryzae. The plants are then placed in agreenhouse at 100% relative atmospheric humidity and 25° C.

Evaluation of the disease infestation is carried out 4 days after theinoculation.

The compounds of preparation Examples 6, 10, 14, 15, 18, 19, 21, 23, 27and 28, for example, show at a compound concentration of 0.025% aninfection degree of 0 to 10%.

It will be understood that the specification and examples areillustrative but not limitative of the present invention and that otherembodiments within the spirit and scope of the invention will suggestthemselves to those skilled in the art.

We claim:
 1. A substituted aminophenyl carbamate of the formula##STR92## in which X represents alkoxycarbonyl with 1 to 6 carbon atomsper alkyl moiety or cycloalkylcarbonyl having 3 to 10 carbon atoms percycloalkyl moiety;Y¹ to Y⁴ are identical or different and representhydrogen, halogen, nitro, cyano, straight-chain or branched alkyl having1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms in thestraight-chain or branched alkyl part and 1 to 9 identical or differenthalogen atoms, alkoxy or halogenoalkoxy, alkylthio, alkylsulfonyl orhalogenoalkylthio in each case having 1 to 6 carbon atoms in thestraight-chain or branched alkyl part, and if appropriate, 1 to 9identical or different halogen atoms; R¹ to R⁷ are identical ordifferent and represent hydrogen, straight-chain or branched alkylhaving 1 to 6 carbon atoms, halogenoalkyl having 1 to 6 carbon atoms inthe straight-chain or branched alkyl part and 1 to 9 identical ordifferent halogen atoms, or alkoxyalkyl having 1 to 6 carbon atoms ineach straight-chain or branched alkyl part; n represents 0 or 1, and Zrepresents straight-chain or branched alkyl or halogenoalkyl each having1 to 6 carbon atoms and, if appropriate, 1 to 9 identical or differenthalogen atoms, or the ##STR93## radical, in which R¹¹ to R¹⁴ areidentical or different and represent hydrogen, straight-chain orbranched alkyl having 1 to 6 carbon atoms, halogenoalkyl having 1 to 6carbon atoms in the straight-chain or branched alkyl part and 1 to 9identical or different halogen atoms, or alkoxyalkyl having 1 to 6carbon atoms in each straight-chain or branched alkyl part, andR¹⁵represents straight-chain or branched alkyl, alkoxyalkyl orhalogenoalkyl each having 1 to 6 carbon atoms in each alkyl part and, ifappropriate, 1 to 9 identical or different halogen atoms,with theproviso that at least one of Y¹ to Y⁴ is halogen.
 2. A substitutedaminophenyl carbamate according to claim 1, in whichR¹ to R⁷ areidentical or different and represent hydrogen or straight-chain orbranched alkyl having 1 to 6 carbon atoms, n represents 0, and Zrepresents straight-chain or branched alkyl or halogenoalkyl each having1 to 4 carbon atoms and, if appropriate, 1 to 5 identical or differenthalogen atoms, or the ##STR94## radical, in which R¹¹ to R¹⁴ areidentical or different and represent hydrogen, straight-chain orbranched alkyl or halogenoalkyl in each case having 1 to 4 carbon atomsand, if appropriate, 1 to 5 identical or different halogen atoms andR¹⁵represents straight-chain or branched alkyl, alkoxyalkyl orhalogenoalkyl in each case having 1 to 4 carbon atoms in each alkyl partand, if appropriate, 1 to 5 identical or different halogen atoms.
 3. Asubstituted aminophenyl carbamate according to claim 1, in whichY¹ to Y⁴are identical or different and represent hydrogen, chlorine, fluorine,bromine, methyl, t-butyl trifluoromethyl or methylsulfonyl, R¹ to R⁷ areidentical or different and represent hydrogen or methyl, n represents 0,and Z represents straight-chain or branched alkyl having 1 to 4 carbonatoms, or the ##STR95## radical, in which R¹¹ to R¹⁴ represent hydrogen,andR¹⁵ represents methyl, ethyl, propyl, butyl, methoxyethyl orethoxyethyl.
 4. A compound according to claim 1, wherein such compoundis 3-chloro-4-(iso-butoxycarbonylamino)-phenylN-(3,6-dioxaheptyl)-carbamate of the formula ##STR96##
 5. A compoundaccording to claim 1, wherein such compound is3-chloro-4-ethoxycarbonylamino)-phenyl N-(3,6-dioxaheptyl)-carbamate ofthe formula ##STR97##
 6. A compound according to claim 1, wherein suchcompound is 2,3-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-methoxyethyl-carbamate of the formula ##STR98##
 7. A compoundaccording to claim 1, wherein such compound is2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-ethyl-3-oxa-butyl)-carbamate of the formula ##STR99##
 8. A compoundaccording to claim 1, wherein such compound is2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-methyl-3-oxa-pentyl)-carbamate of the formula ##STR100##
 9. Acompound according to claim 1, wherein such compound is2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-methyl-3-oxa-butyl)-carbamate of the formula ##STR101##
 10. Acompound according to claim 1, wherein such compound is2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-methoxyethyl-carbamate of the formula ##STR102##
 11. A fungicidalcomposition comprising a fungicidally effective amount of a substitutedaminophenyl carbamate according to claim 1 and a diluent.
 12. A methodof combating fungi which comprises applying to such fungi or to a fungushabitat a fungicidally effective amount of a substituted aminophenylcarbamate according to claim
 1. 13. The method according to claim 12,wherein such carbamate is3-chloro-4-(iso-butoxycarbonylamino)-phenylN-(3,6-dioxaheptyl)-carbamate, 3-chloro-4-ethoxycarbonylamino)-phenylN-(3,6-dioxaheptyl)-carbamate,2,3-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-methoxyethyl-carbamate,2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-ethyl-3-oxa-butyl)-carbamate,2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-methyl-3-oxa-pentyl)-carbamate,2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-(1-methyl-3-oxa-butyl)-carbamate or2,6-dichloro-4-(1-methyl-cyclohexylcarbonylamino)-phenylN-methoxyethyl-carbamate.